KR100285281B1 - Process for producing 3-isothiazolone salt mixture - Google Patents
Process for producing 3-isothiazolone salt mixture Download PDFInfo
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- KR100285281B1 KR100285281B1 KR1019940038782A KR19940038782A KR100285281B1 KR 100285281 B1 KR100285281 B1 KR 100285281B1 KR 1019940038782 A KR1019940038782 A KR 1019940038782A KR 19940038782 A KR19940038782 A KR 19940038782A KR 100285281 B1 KR100285281 B1 KR 100285281B1
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- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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Abstract
Description
본 발명은 3-이소티아졸론염 혼합물의 제조방법에 관한 것으로서, 더욱 상세하게는 유기용매존재하에 N,N′-디메틸-3,3′-디티오디프로피온아미드, 과산화수소 및 염화수소를 반응시켜 방부제나 살균제 등과 같은 바이오사이드(biocide)로서 유용한 다음 구조식(I)로 표시되는 2-메틸-3-이소티아졸론 염산염(이하, MI라 함)과 다음 구조식(II)로 표시되는 5-클로로-2-메틸-3-이소티아졸론 염산염(이하, CMI라 함) 혼합물을 제조하는 개선된 방법에 관한 것이다.The present invention relates to a method for preparing a 3-isothiazolone salt mixture, and more particularly, to react N, N'-dimethyl-3,3'-dithiodipropionamide, hydrogen peroxide and hydrogen chloride in the presence of an organic solvent. 2-methyl-3-isothiazolone hydrochloride (hereinafter referred to as MI) represented by the following structural formula (I) useful as a biocide such as a bactericide, and 5-chloro-2- represented by the following structural formula (II) An improved method of preparing a methyl-3-isothiazolone hydrochloride (hereinafter referred to as CMI) mixture.
상기 구조식(I)과 (II)로 표시되는 MI와 CMI 각각은 안정성 및 약효지속성이 우수한 바이오사이드로서 잘 알려져 있는 바, 이들은 바이오사이드로서 각각 단독으로 사용하는 것보다는 혼합하여 사용할 경우 서로간의 상승효과에 의해 살균력, 항균력, 안정성 및 약효지속성은 더욱 향상된다. 따라서, 이들 혼합물은 냉각탑내의 조류방지제, 도료방부제, 공업용금속가공유 방부제, 화장품첨가제, 샴푸첨가제, 제지용첨가제, 계면활성제 및 농약 등 일반 산업용 방부제는 물론, 항곰팡이제 및 살균제로서도 매우 유용하다.The MI and CMI represented by the structural formulas (I) and (II) are well known as biosides having excellent stability and drug sustainability, and they are synergistic effects of each other when used as a mixture instead of being used alone as biosides. By the bactericidal, antimicrobial, stability and drug sustainability is further improved. Therefore, these mixtures are very useful as antifungal and fungicides as well as general industrial preservatives such as algae inhibitors, paint preservatives, industrial metal-based preservatives, cosmetic additives, shampoo additives, paper additives, surfactants and pesticides in cooling towers.
종래에도 N,N′-디메틸-3,3′-디티오프로피온아미드를 출발물질로 하여 MI와 CMI 혼합물을 제조한 바 있으며[유럽특허 제95,907호], 그 합성방법은 다음 반응식(가)와 같다.Conventionally, a mixture of MI and CMI was prepared using N, N'-dimethyl-3,3'-dithiopropionamide as a starting material [European Patent No. 95,907]. same.
[반응식(가)][Scheme (A)]
상기 종래방법에서는 극성 및 비극성 유기 용매존재하에 상기 구조식(III)으로 표시되는 N,N′-디메틸-3,3′-디티오프로피온아미드에 염소기체를 첨가하여 클로로화 반응(chlorination) 및 고리화 반응(cyclization)에 의해 1:2~3 몰비의 MI와 CMI 혼합물을 제조하였다. 그러나 상기 방법에서는 반응시약으로서 염소기체를 사용하게 되는데, 염소기체는 보관 및 운송이 어렵고 반응 후 여분의 염소기체가 배출되므로 제조방법상 응용범위가 한정되어 있으므로 개선의 여지가 많으며 특히 제조비용이 높아 경제성이 떨어지는 문제가 있다.In the conventional method, chlorination and cyclization are performed by adding chlorine gas to N, N'-dimethyl-3,3'-dithiopropionamide represented by Structural Formula (III) in the presence of polar and nonpolar organic solvents. A mixture of MI and CMI in a 1: 2 to 3 molar ratio was prepared by cyclization. However, in the above method, chlorine gas is used as a reaction reagent. Chlorine gas is difficult to store and transport, and extra chlorine gas is discharged after the reaction. There is a problem of low economic efficiency.
또한 상기 종래방법에서는 중화공정중 Mg(NO3)2의 작용으로 발암물질인 나이트로사민(nitrosamine)이 상당량 발생되며 이를 해결하기 위한 방법으로는 미국특허 제5,137,899호에서 출발물질로 메틸 3-머캅토프로피온산을 사용하여 나이트로사민을 100ppm 미만으로 줄일 수 있었으나 완전히 제거할 수는 없었다.In addition, in the conventional method, a significant amount of nitrosamine, which is a carcinogen, is generated by the action of Mg (NO 3 ) 2 during the neutralization process. As a method for solving this problem, methyl 3-mer is used as a starting material in US Pat. No. 5,137,899. Captopropionic acid could be used to reduce nitrosamines to less than 100 ppm but could not be completely removed.
이에 본 발명의 발명자들은 종래의 MI와 CMI 혼합물의 제조방법에 있어서 염소기체 사용에 따른 제반 문제점을 해결하기 위해 연구 노력한 결과, 염소 기체 대신에 과산화수소와 염산용액을 사용하여 용매내에서 염소기체를 발생시키므로써 본 발명을 완성하였다.Accordingly, the inventors of the present invention have made efforts to solve the problems associated with the use of chlorine gas in the conventional method for preparing a mixture of MI and CMI, and as a result, chlorine gas is generated in the solvent by using hydrogen peroxide and hydrochloric acid solution instead of chlorine gas. This invention was completed.
본 발명은 저렴한 제조비용으로 손쉽게 고수율의 3-이소티아졸론염 혼합물을 제조할 수 있는 새로운 방법을 제공하는데 그 목적이 있다.It is an object of the present invention to provide a novel method for preparing a high yield of 3-isothiazolone salt mixture at low cost.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 용매하에서 N,N′-디메틸-3,3′-디티오프로피온아미드와 염소기체를 반응시켜 다음 구조식(I)로 표시되는 MI와 다음 구조식(II)로 표시되는 CMI 혼합물을 제조하는 방법에 있어서 상기 염소기체 대신에 35% 과산화수소와 35% 염산용액을 사용하는 것을 그 특징으로 한다.The present invention reacts N, N'-dimethyl-3,3'-dithiopropionamide with a chlorine gas in a solvent to prepare a MI mixture represented by the following structural formula (I) and a CMI mixture represented by the following structural formula (II). In the method, 35% hydrogen peroxide and 35% hydrochloric acid solution are used instead of the chlorine gas.
이와같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명은 유기용매 존재하에 N,N′-디메틸-3,3′-디티오프로피온아미드, 염산용액 및 과산화수소를 반응시켜 고순도의 MI와 CMI 혼합물을 제조하는 방법에 관한 것으로서, 그 합성방법을 요약하면 다음 반응식(나)에 나타낸 바와같다.The present invention relates to a method for preparing a high-purity MI and CMI mixture by reacting N, N'-dimethyl-3,3'-dithiopropionamide, hydrochloric acid solution and hydrogen peroxide in the presence of an organic solvent. It is as shown in the following reaction formula (b).
[반응식(나)][Scheme (B)]
상기 구조식(III)으로 표시되는 N,N′-디메틸-3,3′-디티오디프로피온아미드 1몰, 35% 과산화수소 4~8 몰비 그리고 35% 염산용액 10~12 몰비를 유기용매 존재하에 -5~60℃에서 반응시켜 상기 구조식(I)과 (II)의 3-이소티아졸론 염산염 혼합물을 제조한다.1 mole of N, N'-dimethyl-3,3'-dithiodipropionamide represented by the above formula (III), 4-8 mole ratio of 35% hydrogen peroxide and 10-12 mole ratio of 35% hydrochloric acid solution in the presence of an organic solvent. Reaction at ˜60 ° C. to prepare 3-isothiazolone hydrochloride mixtures of formulas (I) and (II).
이때 사용되는 유기용매는 톨루엔, 벤젠, 자일렌, 에틸아세테이트, CH2X2, CHX3, CH2XCH2X 등(여기서, X는 할로겐원자이다.)을 사용하는 것이 바람직하며, 상기 반응온도가 -5℃보다 낮으면 반응시간이 과다하게 길어져 경제성이 없으며, 60℃를 초과하는 경우에는 발열 반응으로 인한 폭발의 위험이 있다.The organic solvent used at this time is preferably toluene, benzene, xylene, ethyl acetate, CH 2 X 2 , CHX 3 , CH 2 XCH 2 X and the like (where X is a halogen atom), the reaction temperature If lower than -5 ℃, the reaction time is excessively long and economical, if it exceeds 60 ℃ there is a risk of explosion due to exothermic reaction.
그리고, 35% 과산화수소가 4 몰비 미만 사용하거나 또는 35% 염산용액이 10몰비 미만 사용되면 미반응물에 의한 수율이 감소하는 문제가 있고, 35% 과산화수소와 35% 염산용액을 상기 몰비 초과하여 사용하는 것은 비경제적이며 또한 부반응에 의한 수율이 감소되는 문제가 있다.In addition, when less than 4 molar ratio of 35% hydrogen peroxide or less than 10 molar ratio of 35% hydrochloric acid solution is used, there is a problem in that the yield by unreacted material is reduced, and using 35% hydrogen peroxide and 35% hydrochloric acid solution in excess of the molar ratio It is uneconomical and there is a problem that the yield by side reactions is reduced.
상기와 같은 본 발명의 제조방법에 의한 경우, 상기 구조식(I)로 표시되는 MI와 상기 구조식(II)로 표시되는 CMI는 1:2.81~3.2 몰비로 제조되는데, 이는 광범위한 살균력과 품질 안정성을 갖는다는 점에서 우수성이 있다.In the manufacturing method of the present invention as described above, the MI represented by the structural formula (I) and the CMI represented by the structural formula (II) are prepared in a molar ratio of 1: 2.81 to 3.2, which has a wide range of sterilizing power and quality stability. It is superior in that it is.
종래에는 MI와 CMI 혼합물을 제조하기 위하여 염소기체 또는 설퍼릴클로라이드(SO2Cl2)와 같은 독성기체를 사용하므로써 과량의 염소기체 또는 아황산기체 발생으로 인하여 작업장을 오염시켰으나, 본 발명에서는 염산용액과 과산화수소를 사용하여 용매속에서 인시츄(in-situ)로 염소기체를 발생시키므로 보다 안전하게 80몰% 이상의 고수율로 목적물을 제조할 수 있다.Conventionally, in order to prepare a mixture of MI and CMI, toxic gas such as chlorine gas or sulfuryl chloride (SO 2 Cl 2 ) is used to contaminate the workplace due to the generation of excess chlorine gas or sulfurous acid gas. Since hydrogen peroxide is used to generate chlorine gas in-situ in the solvent, it is possible to safely produce a target product with a high yield of 80 mol% or more.
또한, 본 발명을 이용하여 중화공정을 시킨 경우는 종래방법에서 문제시되었던 발암물질인 나이트로사민이 전혀 생성되지 않았다.In addition, when the neutralization process was performed using the present invention, nitrosamine, which is a carcinogen which was problematic in the conventional method, was not produced at all.
즉, 본 발명은 과산화수소와 염산용액으로부터 인시츄(in-situ)로 목적화합물을 고수율로 제조하는 방법으로서, 그 공정이 간단하여 매우 경제적이고 부산물이 물외에는 거의 생산되지 않으므로 환경친화적이다.In other words, the present invention is a method of producing a target compound in a high yield in-situ from hydrogen peroxide and hydrochloric acid solution, the process is simple, very economical and environmentally friendly because by-products are hardly produced other than water.
이하, 본 발명을 실시예에 의거하여 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following Examples, but the present invention is not limited by the Examples.
[실시예 1]Example 1
1ℓ 3구 플라스크에 온도계, 드롭핑펀넬 및 교반기를 장착하고, N,N′-디메틸-3,3′-디티오디프로피온아미드 635.8g(0.42 몰)을 톨루엔 108g에 분산시킨 다음 35% 염산용액 364.6ml(4.2 몰)을 가하고 30분간 교반하였다. 반응물의 온도를 0℃로 냉각시킨 후, 드롭핑펀넬을 통해 35% 과산화수소 183.8ml(2.1 몰)를 서서히 가하였다. 드롭핑이 끝나면 30분간 교반시킨 후 교반을 멈추고 정착시킨 다음 반응용액의 pH 4.5가 되도록 수성 MgO 분산액을 가한다. 분액깔대기에 옮겨서 유기층으로부터 수성물질을 분리하고 감압농축한 결과 2-메틸-3-이소티아졸론 염산염(MI)과 5-클로로-2-메틸-3-이소티아졸론 염산염(CMI) 혼합물 137.5g(92 몰%)을 얻었다.A 1 L three-necked flask was equipped with a thermometer, dropping funnel and stirrer, and 635.8 g (0.42 mole) of N, N'-dimethyl-3,3'-dithiodipropionamide was dispersed in 108 g of toluene, followed by 364.6 35% hydrochloric acid solution 364.6 ml (4.2 mol) was added and stirred for 30 minutes. After the reaction was cooled to 0 ° C., 183.8 ml (2.1 mol) of 35% hydrogen peroxide was slowly added through the dropping funnel. After the dropping was completed, the mixture was stirred for 30 minutes, the stirring was stopped, the mixture was settled, and an aqueous MgO dispersion was added until the reaction solution had a pH of 4.5. 137.5 g of a mixture of 2-methyl-3-isothiazolone hydrochloride (MI) and 5-chloro-2-methyl-3-isothiazolone hydrochloride (CMI) as a result of separation of the aqueous substance from the organic layer by concentration in a separatory funnel and concentration under reduced pressure 92 mol%).
[실시예 2~5]EXAMPLES 2-5
상기 실시예 1과 동일한 장치 및 방법에 의해 MI와 CMI 혼합물을 제조하되, 다만 다음 표 1에 나타낸 바와같이 용매의 종류, 염산용액의 사용량 및 과산화수소의 사용량을 달리하였다.The MI and CMI mixture was prepared by the same apparatus and method as in Example 1, except that the type of solvent, the amount of hydrochloric acid solution and the amount of hydrogen peroxide used were different as shown in Table 1 below.
[표 1]TABLE 1
* 선택도(%)= *% Selectivity =
** 수율 : MI와 CMI 혼합물의 수율.** Yield: yield of the MI and CMI mixture.
(1) MI : 2-메틸-3-이소티아졸론 염산염.(1) MI: 2-methyl-3-isothiazolone hydrochloride.
(2) CMI : 5-클로로-2-메틸-3-이소티아졸론 염산염.(2) CMI: 5-chloro-2-methyl-3-isothiazolone hydrochloride.
[실시예 6]Example 6
1ℓ 3구 플라스크에 온도계, 드롭핑펀넬 및 교반기를 장착하고, N,N′-디메틸-3,3′-디티오디프로피온아미드 635.8g(0.42 몰)을 톨루엔 108g에 분산시킨 다음 35% 과산화수소 183.8ml(2.1 몰)을 가하고 30분간 교반하였다. 반응물의 온도를 0℃로 냉각시킨 후, 드롭핑펀넬을 통해 35% 염산용액 364.6ml(4.2 몰)를 서서히 가하였다. 드롭핑이 끝나면 30분간 교반시킨 후 교반을 멈추고 정착시킨 다음 반응용액의 pH 4.5가 되도록 수성 MgO 분산액을 가한다. 분액깔대기에 옮겨서 유기층으로부터 수성물질을 분리하고 감압농축한 결과 MI와 CMI 혼합물 139g(93 몰%)을 얻었다.A 1 L three-necked flask was equipped with a thermometer, dropping funnel and stirrer, and 635.8 g (0.42 mole) of N, N'-dimethyl-3,3'-dithiodipropionamide was dispersed in 108 g of toluene and 183.8 ml of 35% hydrogen peroxide (2.1 mol) was added and stirred for 30 minutes. After the reaction was cooled to 0 ° C., 364.6 ml (4.2 mol) of 35% hydrochloric acid solution was slowly added through the dropping funnel. After the dropping was completed, the mixture was stirred for 30 minutes, the stirring was stopped, the mixture was settled, and an aqueous MgO dispersion was added until the reaction solution had a pH of 4.5. Transfer to a separatory funnel to separate the aqueous material from the organic layer and concentrated under reduced pressure to give 139g (93 mol%) of MI and CMI mixture.
[실시예 7~10]EXAMPLES 7-10
상기 실시예 6과 동일한 장치 및 방법에 의해 MI와 CMI를 제조하되, 다만 다음 표 2에 나타낸 바와같이 용매의 종류, 염산용액의 사용량 및 과산화수소의 사용량을 달리하였다.MI and CMI were prepared by the same apparatus and method as in Example 6, except that the type of solvent, the amount of hydrochloric acid solution and the amount of hydrogen peroxide used were different as shown in Table 2 below.
[표 2]TABLE 2
* 선택도(%)= *% Selectivity =
** 수율 : MI와 CMI 혼합물의 수율.** Yield: yield of the MI and CMI mixture.
(1) MI : 2-메틸-3-이소티아졸론 염산염.(1) MI: 2-methyl-3-isothiazolone hydrochloride.
(2) CMI : 5-클로로-2-메틸-3-이소티아졸론 염산염.(2) CMI: 5-chloro-2-methyl-3-isothiazolone hydrochloride.
[실시예 11]Example 11
1ℓ 3구 플라스크(1)에 온도계, 드롭핑펀넬 및 교반기를 장착하고, 또 다른 1ℓ 3구 플라스크(2)에 드롭핑펀넬 및 교반기를 장착시킨 후 유리관을 통해 발생기체가 플라스크(1)로 이동하도록 장치하였다. 플라스크(1)에 N,N′-디메틸-3,3′-디티오디프로피온아미드 635.8g(0.42 몰)을 톨루엔 108g에 분산시킨다. 플라스크(2)에 35% 과산화수소 183.8mL(2.1몰)을 가하고 30분간 교반한 후, 드롭핑펀넬을 통해 35% 염산용액 364.6ml(4.2 몰)를 서서히 가하였다. 드롭핑이 끝나고 계속 교반하여 침전물이 생성되면 교반을 멈추고 침전물을 여과하여 수거한 다음, 진공오븐에서 50℃로 3시간동안 건조시킨 결과 MI와 CMI 혼합물 137.6g(92 몰%)을 얻었다.A 1 liter three-necked flask (1) is equipped with a thermometer, a dropping funnel and an agitator, and another 1 liter three-necked flask (2) is equipped with a dropping funnel and an agitator, and then the generator gas is transferred to the flask (1) through a glass tube. It was set up to. In the flask 1, 635.8 g (0.42 mol) of N, N'-dimethyl-3,3'-dithiodipropionamide was dispersed in 108 g of toluene. 183.8 mL (2.1 mol) of 35% hydrogen peroxide was added to the flask (2), stirred for 30 minutes, and then 364.6 ml (4.2 mol) of 35% hydrochloric acid solution was slowly added through a dropping funnel. After dropping, stirring continued and a precipitate was formed. The stirring was stopped, the precipitate was collected by filtration, and dried in a vacuum oven at 50 ° C. for 3 hours to obtain 137.6 g (92 mol%) of a mixture of MI and CMI.
[실시예 12~15][Examples 12-15]
상기 실시예 11과 동일한 장치 및 방법에 의해 MI와 CMI 혼합물을 제조하되, 다만 다음 표 3에 나타낸 바와같이 용매의 종류, 염산용액의 사용량 및 과산화수소의 사용량을 달리하였다.A mixture of MI and CMI was prepared by the same apparatus and method as in Example 11, except that the type of solvent, the amount of hydrochloric acid solution and the amount of hydrogen peroxide used were different.
[표 3]TABLE 3
* 선택도(%)= *% Selectivity =
** 수율 : MI와 CMI 혼합물의 수율.** Yield: yield of the MI and CMI mixture.
(1) MI : 2-메틸-3-이소티아졸론 염산염.(1) MI: 2-methyl-3-isothiazolone hydrochloride.
(2) CMI : 5-클로로-2-메틸-3-이소티아졸론 염산염.(2) CMI: 5-chloro-2-methyl-3-isothiazolone hydrochloride.
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